Lewis acid mediated asymmetric [2,3]-sigmatropic rearrangement of allylic amines. Scope and mechanistic investigation

被引：26
作者：
Blid, Jan [1 ]
Panknin, Olaf [1 ]
Tuzina, Pavel [1 ]
Somfai, Peter [1 ]
机构：
[1] KTH Chem Sci & Engn, SE-10044 Stockholm, Sweden
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 72卷 / 04期
关键词：
D O I：
10.1021/jo062178v
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
[GRAPHIC] The first asymmetric [2,3]-sigmatropic rearrangement of achiral allylic amines has been realized by quaternization of the amines with an enantiomerically pure diazaborolidine and subsequent treatment with Et3N. The resultant homoallylic amines were obtained in good yields and excellent ee's. The observed diastereo- and enantioselectivities were rationalized by invoking a kinetically controlled process, and support for this model was obtained from an NMR spectroscopic investigation of the chiral Lewis acid-substrate complex. The structure of the Lewis acid-product complex was established by X-ray crystallographic analysis and supported the proposed mechanism.
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页码：1294 / 1300
页数：7
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